Production of sulphonates of tertiary alcohols



Patented June 15, 1937 UNITED TE PATENT I E 2,984,253 v p v Anton Hintermaier, Dusseldorf, Germany, assignor to the firm Henkel & Cie, Gesellschaft mit beschriinkter Hattun g, Dusseldorf, Germany No Drawing. Application April 28,1934, Serial No. 722,966. In Germany August 2, 1933 10 ClaimSr (Cl. 260-459).

Sulphonation products of tertiary alcohols are already known, the tertiary alcohols being first 1,

converted into oleflnes, which are then converted, mto sulphonation products by treatment with 5 sulphuric acid of varying water-content. The

resulting acid sulphuric esters are very unstable and to some extent are so unstable that they are hydrolyzed even by the moisture of the air. Owe ing precisely totheir hold.

This invention relates to a process for sulpho-e I nating tertiary alcohols, which are substituted at the tertiary carbon atom with at least one long chain higher aliphatic and/or atleast one hydroaromatic radical, or derivatives of such alcohols,

in such a manner asto form true sulphonic acids which are not only water-soluble but are also. stable to hydrolysis. The process comprises treating the said tertiary alcohols, or; their derivatives,- with strongly sulphonating and dehydrating,

agents. Sulphonating agents within the mean+fing of the invention comprise sulphonating agents which have both asulphonating a dehydrating 5 action, such as oleum and chlorosulphonic acid,

halogen sulphonicacids; and also mixtures vof sulphonating substances and dehydrating substances. Among such dehydrating substances may be mentioned for example: Simple or mixed acid anhydrides of inorganlcor organic acids,

2 such as for example, acetic anhydride, acid hal-- ides, for example acetyl chloride, phosphorus hal-i ides, and also dehydration products of hydrox'yl-- containinglacids' of the type of pyro or meta acids or their salts, furthermore, salts having a.

dehydrating action and the like.- Mixtures of concentrated sulphuric acid and acetic anhydride, or of sulphuric acid containing S03 and acetic acid, are suitable. If desired, the sulph'o- 40 nation can be carried out with the further addition of solvents or 'sulphonation accelerators. Among the substances which come into consideration as starting materials are the tertiary alw I instability, such products 10 cannot be employed in industry or in the house-i .or other substances the herein-mentioned dehydrating agents and" then, after reaction has taken place, the sulphonating agents.

The high-moleculartrue sulphonicacids ob tained according" to the invention are remarkable among other things for their considerable vwetting and emulsifying action, and are therefore excellent for use as capillary-active or surface-active agents, more particularly as wetting, washing, cleansing, emulsifyingand dispersing agents.

Preferably, the sulphonic acids of unsaturated tertiary carbinols, and of mixturesof homclo-j gous-compoundshave been'iound'to be suitable.

More'particularly, thesalts of the said sulphonic acids, for example the sodium, potassium or triethariolamine salts or the'saltsof other amines may employed for the purposes spear-f 'It has been tbundtnat the said compounds may be employed advantageously wherever the capillary-active properties of liquids, more par+ ticularly aqueous liquids, are to be enhanced; Due totheir capillaryeactive properties, thecompounds may be employed for example for foamproduction, emulsifying, dispersing, limpregnating, peptizing, stabilizing, levelling, distributing,

dissolving and the like in many different industries. They may as ssistants inithe leather, ticularly in the textile industry in many difler-I ent working processes. The said substances exhibit their activity also in admixture with other substances; thus, apart from, gthese substances,- other additions, for example, alkaline agents, per-compounds, super-V fatting agents and the like may be added to the treatment baths. They may be employed in acid,

neutral and alkaline liquids and baths, and also in. baths containing which render water hard. They-may be employed either alone or in admixture with other wetting, washing, cleansing, emul-' sifying and dispersing agents; 'furthermore;'there" may be added to the said compounds, for example per-compounds, such as perborates, persulphates and percarbon-ates, or alkaline agents such as soda, trisodium phosphate, water glassand borax, or neutral agents, such as sodium sulphate, or even acid agents, such as acid sodium;

sulphate. 7

Also, the compounds maybe employed in ad such as organic hydromixture with solvents, carbons, alcohols and the like or in admixture with enzymes, such as urease and pancreatin; The agents manufactured with a content of be employed for' example" fur and more paraelectrolytes, lime, magnesia the new compounds may be put on the market in the solid iorm, ior example in the iorm of powders, flakes, lumps or shreds or the like, and also ior household purposes. They may; however, be put on the market already dissolved in liquids, or in the form oi pastes andcreams, such as ior example in cosmetickpreparations,

polishing agents, soap creams and the like.

The liquids manufactured with the said agents may be employed either in the hot or cold state.

a E's-ample i 7 Into 50 parts oi undecyl diethyl carbinol, which have been-dissolved in 50 parts oi acetic anhy'-' dride, are introduced in drops50 parts oi concentrated sulphuric acidwhile stirring and cooling by ice. The sulphonation "is completedby heating to room temperature. The resulting vls- A cous solution is poured upon ice and the mass is then mixed with 100 parts oi butanol.

The aqueous layer, which contains .the-bulk oi'the acid, is separated. The butyl alcohol solution oi the sulphonation product is neutralized by means of sodium bicarbonate. Aiter separating the resulting precipitate, the filtrate is evaporated down in a-vacuum.

E'samplez For the r the better levelling or acid wool dyes, 0.2 to 0.5 per cent oi the oi the sulphonation product oi a mixture oi higher carbinols, which correspond to the soya fatty acids and aresubstituted at thejcarbinol carbon atom by 2, ethyl groups, added to the dyeing bath. The said sulphonatlonproduct is] remarkable'ior its excellent wetting power. [It

The 'eil'ect-occurs in is stable to lime and acid. the treatment both oi piece goods and .oigoods inthehan'k... g n j Y Example) In dyeing artificial sillr'inaterials, whichexhibit a tendency to unevenness, for example in dyeing stockings on apparatus, about 0.4 to 0.6

per cent. oi the sodium salt oi the sulphonation product or a mixture oi" higher carbinols, which correspondto whale oil fatty. acids and are sub-j stituted at the vcarbi'nol carbon atom by 2 methyl soods are sroups, is'added to the bath. The wetted right through and dyed evenly.

7 Example 4 In bucking, 0.1 to 0.3 percent oi the sodium salt oi the sulphonation product of a,mixture oi higher carbinols,,which correspond to the soya oil fatty acids and are substituted at the carbinol carbon atom by 2 methyl groups, 'is added to the bath. Due to the stability of the sulphonation product to lime, lime deposits are prevented. A very even fabric is obtained.

The product may, also be employed with equal success as an addition to mercerizing lyes.

1 Example 5 The sodium salt oi thesulphonation product oi a mixture oihigher carbinols, which correspond to linseed oil fatty acids and are substituted at the carbine] carbon atom by 2 ethyl groups, is added to an alkaline cleansing agent in order to enhance the wetting power. The

agent may be employed, more particularly in automatic machines, where, it is important to prevent the formation of ioamas far as possible but where an excellent cleansing and-wetits stability to lime and I oi a mixture or higher *ous solutions exhibit molecular true sulphonic acid tiary alcohols, which are it is remarkable to: acid, and its ready Example 0.

The sodium salt oi the osrbinols, which correspond to the sperm oil iattyacids and are substituted at the carbinol carbon atom by 2 methyl groups. may be employed very succsssiully tor the manuiacture oi sizes and finishes. Its aqueting power is desirable.

solubility.

with regard to textiles, such as cotton and wool.

Owing to its pronounced stability to lime, the

sulphonation product may also be employed with very hard 4 7 Sample 7 g The triethanolamine salt oi the sulphonation productoi a mixture oi higher carbinols, which correspond to the coconut oil iatty acids and m are substituted at the carbine! carbon atom by 3 methylgroups, is excellent ior use tor the manuiacture oi emulsions, which can be used nsspim ping lubricants, floor P lishing compositions and I claim: f '1. The process ior the minimum emet- -molecular true sulphonio which comprises treating with'm'ongly: snip I and dehydrating agents mixtures of homologous tertiary alcohols, which are from glyeerides oi acids having higher fliphatic'radicals, by the action 0! magnesium halogen alkyla;

2. The process described in-claim said acid is an unsaturated fatty acid.

3. The process ior the mamnactureoi high molecular true sulphonic acid'products, wherein" n a mixture oi homologous tertiary alcohols, which are'produced from glycerides "or aciik having, higher aliphatic radicals, bytheaction oi msgnesium halogen" alkylqis treated first with. dehydrating agent and thenwith a agent. i i 4. The process ior 'oihighmolecular true suiphonic acid products. wherein 4| a oihomologous which are produced- :iroin giyoerides of acids higher aliphatic radicals, by theaction oi msgnesium alkyls. is treated ilrst'with debsdrating agents and then with and 5. The process ior' the manuiacture'oi high-' comprises treating a mixture or homologous te'r- V I produced from glyeerides of acids having higher aliphatic radicals, by the action oi magnesium halogen lime. with sulphonating and dehydrating in the presence sulphonation product 6 io' aremarkablewettingpower drating agents and with agents having both a dehydrating and sulphonating action.

8. A new product of manufacture consisting oi. a high-molecular true sulphonic acid product obtained by treating with strongly sulphonating and dehydrating agents a mixture of homologous tertiary alcohols, which are produced from glycerides of acids having higher aliphatic radicals, by

the action or magnesium halogen alkyls.

9. A new product 01 manuiacture consisting of a .water-soluble salt of a high-molecular true 

